A hyperbranched polysiloxane modified abrasion resistant thermoplastic elastomer and a method of making the same

Abstract

The application relates to the technical field of high polymer composite materials and thermoplastic elastomer modification, and discloses a wear-resistant thermoplastic elastomer and a preparation method thereof. The thermoplastic elastomer is composed of a thermoplastic elastomer matrix and a wear-resistant modification component dispersed in the matrix, the wear-resistant modification component comprises bio-based hyperbranched polysiloxane, nano ceramic particles and short-cut glass fibers; wherein the bio-based hyperbranched polysiloxane forms a semi-interpenetrating polymer network with the matrix, the short-cut glass fibers form a microfiber structure in a melting process, and a reversible dynamic covalent crosslinking structure is further introduced into the matrix, so that the material has certain network reconstruction and self-repairing capacity under the action of friction heat. The application also discloses a corresponding preparation process. The material has low abrasion, low friction coefficient, high tensile strength, high elongation at break and good self-repairing performance, and is suitable for the preparation of products such as wear-resistant sealing parts, wear-resistant conveying components and flexible protection components.

Description

Technical Field

[0001] This invention relates to the field of packaging film technology made of polyvinyl chloride material, and more specifically, to a medical sterile packaging film with tear resistance and its preparation process. Background Technology

[0002] Thermoplastic elastomers combine the elastic characteristics of rubber with the processing properties of thermoplastic resins, and are widely used in footwear, seals, cushioning pads, conveyor components, wire and cable sheaths, and automotive interior and exterior parts. With increasingly complex service conditions, these products, subjected to repeated friction, compression, bending, and heat accumulation, often need to maintain not only good flexibility and mechanical strength, but also low wear, stable friction behavior, and a long service life. Therefore, how to further improve the wear resistance of thermoplastic elastomers while ensuring their processing performance and elastic recovery has become an important issue in the modification research of this type of material.

[0003] In existing technologies, improving the wear resistance of thermoplastic elastomers often involves directly adding inorganic fillers, fiber reinforcements, or low surface energy additives to the matrix. For example, Chinese patent CN105131536B discloses a high-wear-resistant TPEE thermoplastic polyester elastomer. Its main technical solution involves compounding PTFE, lubricants, antioxidants, and silica particles of a specific gradation into the TPEE system to improve the material's wear resistance, resilience, toughness, and resistance to chemical media. The key technical focus lies in further improving impact and friction resistance through the synergistic buffering and reinforcing effects of silica with different particle sizes, as well as the design of the porous structure and surface coupling treatment of the silica.

[0004] For example, Chinese patent application CN119662013A discloses a wear-resistant thermoplastic elastomer material for cable sheaths. Its core is the compounding of polyethylene glycol, fine-grained clay, silane coupling agents, and stabilizing additives into a thermoplastic polyurethane system to balance wear resistance, flexibility, and mechanical properties. The preparation method is relatively simple, mainly achieved through additive formulation, mixing, and extrusion granulation. Furthermore, it demonstrates that the compounding of polyethylene glycol and clay and the control of their weight ratio are key to improving tensile strength, elongation at break, and reducing wear volume.

[0005] However, neither of the existing elastomers represented by these two technologies can solve the problem of reversible dissociation and recombination after localized damage, microcrack initiation, or interfacial relaxation, thereby slowing down the continuous degradation of material properties over service time. This leads to a gradual decline in wear resistance and mechanical properties during use. Therefore, developing a wear-resistant thermoplastic elastomer material that can balance wear resistance, mechanical properties, elastic recovery, and a certain degree of self-healing ability has significant practical application value. Summary of the Invention

[0006] To achieve the above objectives, the present invention provides the following technical solution: a hyperbranched polysiloxane-modified wear-resistant thermoplastic elastomer, wherein the thermoplastic elastomer is composed of a wear-resistant composite material, the composite material comprising: The thermoplastic elastomer matrix accounts for 68.5% to 83.33% of the total mass of the composite material. A wear-resistant modifying component dispersed in the thermoplastic elastomer matrix, the wear-resistant modifying component comprising: Hyperbranched polysiloxanes, with a mass of 3% to 25% of the thermoplastic elastomer matrix; Nano-ceramic particles with a particle size of 50–100 nm, whose mass is 2%–20% of the thermoplastic elastomer matrix; and Short-cut glass fibers, with a mass of 1% to 10% of the thermoplastic elastomer matrix; The hyperbranched polysiloxane forms a semi-interpenetrating polymer network with the thermoplastic elastomer matrix, and the chopped glass fibers form microfiber structures in situ during the melt processing and are dispersed in the matrix; the aspect ratio of the microfiber structure is (50:1) to (100:1), the diameter distribution range of the microfibers is 6μm to 13μm, and the microfibers are distributed in a three-dimensional network in the matrix.

[0007] Further, the thermoplastic elastomer matrix is ​​at least one of thermoplastic polyurethane, thermoplastic polyester elastomer, thermoplastic polyamide elastomer, or styrene-based thermoplastic elastomer; the hyperbranched polysiloxane is a bio-based hyperbranched polysiloxane, which contains reactive functional groups at its ends, wherein the reactive functional groups are selected from hydroxyl, amino, or epoxy groups, and the bio-based carbon content is not less than 25% (i.e., the carbon content in the bio-based polyol is not less than 25%). The raw materials for preparing the bio-based hyperbranched polysiloxane include, by weight: 10-50 parts by weight of bio-based polyol, wherein the bio-based polyol is selected from one or more of glycerol, glucose, plant-derived polyols, citric acid, lactic acid or their derivatives; 5-30 parts by weight of silane coupling agent, wherein the silane coupling agent is selected from one or more of methyltriethoxysilane (MTES), aminotriethoxysilane (APS), vinyltrichlorosilane (VCTS) or triethoxysilane acrylate (AEOS); 0.5 to 5 parts by weight of acid catalyst, wherein the acid catalyst includes, but is not limited to, sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, phosphoric acid or boron trifluoride; 1 to 5 parts by weight of a reactive functional group modifier, wherein the reactive functional group modifier includes, but is not limited to, isocyanate compounds, epoxy compounds, carboxylic acid compounds or aldehyde compounds; The organic solvent is 10 to 100 parts by weight, and the organic solvent is an ether organic solvent, chloroform or anhydrous ethanol, including but not limited to tetrahydrofuran (THF) and dimethyl thionamide (DMSO).

[0008] Furthermore, the preparation method of the bio-based hyperbranched polysiloxane includes the following steps: A1: Mix the bio-based polyol and the silane coupling agent in the specified weight parts evenly to obtain a reaction mixture; A2: Add the reaction mixture obtained in step A1 to the organic solvent in the specified weight, heat to 120-200°C, and stir continuously at 100-500 rpm for 1-4 hours to ensure uniform reaction; A3: Add the acid catalyst in the specified weight amount to the reaction intermediate obtained in step A2, and continue heating to 150-200°C to allow the reaction to undergo polycondensation and form hyperbranched polysiloxane. The reaction time is 3-6 hours. A4: After the reaction in step A3 is completed, the reactive functional group modifier in the specified weight amount is added to the reaction product of step A3 to terminate the reaction and end-functionalize the hyperbranched polysiloxane; the reactive functional group modifier is used to react with the end functional groups of the bio-based hyperbranched polysiloxane to perform end-functionalization modification. A5: After the reaction is complete, the system is cooled to 20-30℃, and then excess organic solvent is slowly removed to obtain a bio-based hyperbranched polysiloxane preproduct. The preproduct is then dried at 60-80℃ for 4-12 hours to obtain the bio-based hyperbranched polysiloxane.

[0009] Furthermore, the isocyanate compound is one or more of methyl isocyanate and toluene-2,4-diisocyanate, used for reaction with amino groups; The epoxy compound is one or more of epoxy acrylate and epichlorohydrin, and is used to react with hydroxyl groups; The carboxylic acid compound is one or more of benzoic acid and adipic acid, and is used to react with amino groups; The aldehyde compound is one or more of formaldehyde and pentenal, and is used to react with amino and hydroxyl groups.

[0010] Furthermore, the nano-ceramic particles are one or more of silicon nitride (Si3N4) nanoparticles, aluminum nitride (AlN) nanoparticles, aluminum oxide (Al2O3), silicon carbide (SiC) nanoparticles, or zirconium oxide (ZrO2) nanoparticles.

[0011] Furthermore, the thermoplastic elastomer matrix is ​​a thermoplastic elastomer matrix with a dynamically covalently crosslinked structure, which is formed by preparing the following raw material components: The difunctionalized copolymer component A containing a reversible Diels-Alder structure (cycloaddition reaction, i.e., the structure obtained by the Diels-Alder reaction) is used in an amount of 1% to 15% by weight of the thermoplastic elastomer matrix. The difunctionalized copolymer component A is a polyether polyol with furan end groups or a polyether polyol polyester polyol with furan end groups. The amount of dienophilic crosslinking agent component B, by weight, is 0.5% to 10% of the mass of the thermoplastic elastomer matrix; the dienophilic crosslinking agent component B is a maleimide difunctionalized small molecule or a polymer containing dimaleimide groups; The diboronic acid crosslinking agent component C, by weight, is used in an amount of 0.1% to 8% of the mass of the thermoplastic elastomer matrix, wherein the diboronic acid crosslinking agent component C is phenyl 1,4-diboronic acid or its ester derivative. The hydroxyl functional modification component D, by weight, is used in an amount of 0.5% to 10% of the mass of the thermoplastic elastomer matrix, wherein the hydroxyl functional modification component D is a modified isoprene in which 1,2-diol or 1,3-diol segments can be introduced. Catalyst component E, by weight, is used in an amount of 0.01% to 2% of the mass of the thermoplastic elastomer matrix, and catalyst component E is a Lewis acid catalyst; The amount of the thermoplastic elastomer matrix is ​​as defined in claim 1.

[0012] The prepared thermoplastic elastomer matrix also contains a dynamic covalent crosslinking structure. The dynamic covalent crosslinking structure forms a reversible Diels-Alder bond by introducing compounds containing furan groups and maleimide groups, or forms a reversible borate ester bond with the hydroxyl groups in the matrix by introducing compounds containing boric acid groups. The dynamic covalent crosslinking structure can reversibly dissociate and recombine under frictional heat, giving the material self-healing properties.

[0013] Furthermore, the method for preparing the thermoplastic elastomer matrix with the dynamically covalently crosslinked structure includes: 1) Mix the corresponding mass of thermoplastic elastomer matrix with the corresponding mass of the difunctional copolymer component A and the corresponding mass of the hydroxyl functional modified component D in a mixer at a temperature of 80-180°C and a speed of 50-200 rpm for 10-30 minutes to achieve uniform mixing. 2) Heat the mixture to 120-180°C under a nitrogen atmosphere and stir at 50-300 rpm to allow the matrix and component D to pre-react, producing polymer segments that can react with the dienophilic crosslinking agent component B and the diboronic acid crosslinking agent component C added in step 3). 3) Add the appropriate mass of the dienophilic crosslinking agent component B and the appropriate mass of the diboronic acid crosslinking agent component C to the mixture obtained in step 2), and react at 140-200°C for 1-6 hours to form a dynamic covalent crosslinking network with reversible Diels-Alder reversible crosslinking points and borate ester reversible crosslinking points; 4) Add the corresponding mass of the catalyst component E to the mixture obtained in step 3), and carry out the catalytic crosslinking reaction at 150~200℃ for 1~4 hours to fully generate the reversible crosslinking network while suppressing unnecessary side reactions; 5) Finally, the product obtained in step 4) is cooled to room temperature to obtain a thermoplastic elastomer matrix with a dynamic covalent crosslinking structure, wherein the dynamic covalent crosslinking structure can be thermally reversed and recombined.

[0014] Further, the thermoplastic elastomer matrix is ​​at least one of thermoplastic polyurethane, thermoplastic polyester elastomer, thermoplastic polyamide elastomer, or styrene-based thermoplastic elastomer; The difunctionalized copolymer component A is furan-terminated polytetrahydrofuran diol, furan-terminated polypropylene glycol diol, furan-terminated polycaprolactone diol, furan-terminated polycarbonate diol, and furan-terminated poly(adipate-butanediol) polyester diol. The dienophilic crosslinking agent component B is 1,4-bis(maleimide)butane or 1,6-bismaleimidehexane. 、 One or more of bismaleimide polyethylene glycol, four-armed polyethylene glycol-maleimide, or eight-armed polyethylene glycol-maleimide; The binary boric acid crosslinking agent component C is one or more of phenyl-1,4-diboronic acid, phenyl-1,4-diboronic acid methyliminodiacetic acid ester, 1,4-phenyldiboronic acid bis(neopentyl glycol) ester or phenyl-1,4-diboronic acid methyliminodiacetic acid ester. The hydroxyl functional modification component D is one or more of hydroxyl-terminated polyisoprene diol, polyisoprene-based hydroxyl polymer, or polyisoprene difunctional hydroxyl polymer. The catalyst component E is one or more of aluminum trifluoride, zinc chloride, boron chloride, ferric chloride, boron trifluoride, titanium trichloride, or phosphorus pentachloride.

[0015] This application also provides a method for preparing the hyperbranched polysiloxane-modified wear-resistant thermoplastic elastomer as described above, comprising the following steps: S1: Using bio-based polyols as the core molecule, terminally functionalized hyperbranched polysiloxanes are synthesized through stepwise polycondensation reactions. S2: The thermoplastic elastomer matrix of a corresponding mass fraction, the chopped glass fiber of a corresponding mass fraction, the hyperbranched polysiloxane prepared in step S1 of a corresponding mass fraction, and the nano-ceramic particles with a particle size of 50-100 nm of a corresponding mass fraction are dynamically vulcanized and melt-blended in an extruder. The temperature of the dynamic vulcanization and melt blending is 150℃-280℃, the screw speed is 200rpm-1000rpm, and the residence time is 2min-10min, so that the nano-ceramic particles and chopped glass fiber are uniformly dispersed in the thermoplastic elastomer matrix, and a wear-resistant thermoplastic elastomer composite material is formed at the same time. S3: The wear-resistant thermoplastic elastomer composite material obtained in step S2 is molded into the wear-resistant thermoplastic elastomer.

[0016] Furthermore, the compression molding step includes: injecting the wear-resistant thermoplastic elastomer composite material obtained in step S2 into the mold within a time of 15 seconds to 60 seconds at an injection pressure of 180℃~240℃ and 30MPa~80MPa, and cooling for 2min~6min after injection to complete the compression molding; the entire cycle time from injection to cooling is 3min~8min.

[0017] The present invention has the following beneficial effects: 1. This application introduces bio-based hyperbranched polysiloxanes into a thermoplastic elastomer matrix, enabling the formation of a more stable semi-interpenetrating network structure within the material. Due to the numerous branched segments and terminal functional groups of the hyperbranched polysiloxanes, they not only improve compatibility and interfacial bonding with the matrix but also promote the formation of a more stable low-shear interface layer on the surface during friction, thereby reducing frictional resistance and mitigating surface wear. Compared to conventional linear siloxane modification methods, this structure is more advantageous in maintaining material flexibility while simultaneously achieving friction reduction and structural stability during friction.

[0018] 2. This application disperses nano-ceramic particles in a thermoplastic elastomer matrix and modulates the particle interface using hyperbranched polysiloxanes, making it easier for the nano-ceramic particles to maintain a fine dispersion state within the material. The nano-ceramic particles can improve the material's surface resistance to cutting and plastic deformation, and reduce the tendency for local surface collapse and groove expansion during frictional contact. Because the particle size is at the nanoscale and the interfacial bonding with the matrix is ​​relatively stable, it can improve the material's wear resistance and structure retention during friction without significantly sacrificing material ductility.

[0019] 3. This application uses chopped glass fibers as the reinforcing component, forming a microfiber structure during the melt processing. This microfiber structure, distributed three-dimensionally within the matrix, constitutes a relatively continuous reinforcing skeleton, distributing loads and delaying crack propagation in the initial stages of material stress or frictional damage. The microfibers also exert traction and transfer effects on localized stress, reducing stress concentration in wear areas and enabling the material to maintain good mechanical support under repeated friction and alternating deformation conditions, thus balancing wear resistance, tensile strength, and dimensional stability.

[0020] 4. This application further constructs a reversible dynamic covalent cross-linked structure within the thermoplastic elastomer matrix, enabling the material to possess a certain network reconstruction capability under frictional heat or external thermal stimulation. This dynamic network can reversibly dissociate and recombine after localized damage, microcrack initiation, or interfacial relaxation, thereby mitigating the problem of continuous performance degradation over time. Compared with traditional systems relying solely on static filler reinforcement, the material of this application not only exhibits better initial wear resistance but also can restore the structural continuity and mechanical response of damaged areas to a certain extent, improving the long-term reliability of the material.

[0021] 5. This application achieves a good overall balance between wear resistance, frictional stability, tensile strength, elongation at break, and self-healing ability through the combined effects of bio-based hyperbranched polysiloxane, nano-ceramic particles, microfiber reinforced structure, and dynamic covalent cross-linked network. This technical solution does not simply improve a single indicator, but rather enhances the overall performance of the material under complex friction conditions while ensuring the processing performance and elastic recovery ability of the thermoplastic elastomer. Therefore, it is more suitable for wear-resistant seals, flexible conveying components, protective buffer components, and other products that require both flexibility and wear resistance. Attached Figure Description

[0022] Figure 1 The microscopic morphology of the cross-section formed by melt shearing of short glass fibers in the wear-resistant thermoplastic elastomers obtained in Examples 1-3 is shown. Figure 2 The microstructure of the cross-section formed by melt shearing of short glass fibers in the wear-resistant thermoplastic elastomers obtained in Comparative Examples 1-3 is shown. Detailed Implementation

[0023] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0024] The chemical reagents and related equipment used in the embodiments of this application are all commercially available, and some tests can be completed by a testing agency.

[0025] Example 1 This embodiment provides a wear-resistant thermoplastic elastomer. The wear-resistant thermoplastic elastomer uses thermoplastic polyurethane as the base resin, and constructs a dual dynamic covalent cross-linked structure within the base resin. Simultaneously, bio-based hyperbranched polysiloxane, nano-ceramic particles, and chopped glass fibers are introduced to form a wear-resistant reinforcing system.

[0026] (I) Preparation of bio-based hyperbranched polysiloxanes Weigh out 10 parts by weight of glycerin, 18 parts by weight of aminotriethoxysilane, 5 parts by weight of p-toluenesulfonic acid, 1 part by weight of epichlorohydrin and 55 parts by weight of anhydrous ethanol.

[0027] Glycerol and aminotriethoxysilane were first mixed thoroughly to obtain a reaction mixture. This reaction mixture was then added to anhydrous ethanol and stirred at 320 rpm for 4 hours at 120°C. Next, p-toluenesulfonic acid was added, and polycondensation was continued at 185°C for 3 hours. After the reaction was complete, epichlorohydrin was added to modify the terminal functional groups. The system was then cooled to 30°C to remove excess solvent and dried at 60°C for 12 hours to obtain a bio-based hyperbranched polysiloxane with terminal epoxy and partially amino functional groups.

[0028] (II) Preparation of thermoplastic elastomer matrix with dynamic covalent crosslinking structure In this embodiment, the thermoplastic elastomer matrix accounts for 80% of the total mass of the final hyperbranched polysiloxane-modified wear-resistant thermoplastic elastomer, the bio-based hyperbranched polysiloxane accounts for 3% of the mass of the thermoplastic elastomer matrix, the nano-ceramic particles account for 12% of the mass of the thermoplastic elastomer matrix, and the chopped glass fibers account for 10% of the mass of the thermoplastic elastomer matrix. The microfiber structure formed after melt processing has an aspect ratio of 50:1 and a microfiber diameter of 13 μm.

[0029] Based on 100 parts by weight of thermoplastic polyurethane base resin, 15 parts by weight of furan-terminated polytetrahydrofuran diol are added as component A, 2 parts by weight of 1,4-bismaleimide butane as component B, 1 part by weight of benzene-1,4-diboronic acid as component C, 4 parts by weight of hydroxyl-terminated polyisoprene diol as component D, and 0.10 parts by weight of zinc chloride as component E.

[0030] First, the thermoplastic polyurethane base resin, component A, and component D were mixed at 80°C and 200 rpm for 10 min. Then, under a nitrogen atmosphere, the temperature was raised to 180°C, and a pre-reaction was carried out with stirring at 90 rpm. Next, components B and C were added, and the reaction was carried out at 140°C for 6 h to form a reversible Diels-Alder structure, i.e., reversible Diels-Alder crosslinking points, and to generate reversible borate ester crosslinking points. Then, component E was added, and a catalytic reaction was carried out at 170°C for 1 h. After the reaction was completed, the mixture was cooled to room temperature to obtain a thermoplastic polyurethane matrix with a dynamically covalently crosslinked structure. (III) Preparation of wear-resistant thermoplastic elastomers Based on 100 parts by weight of the above-mentioned thermoplastic elastomer matrix with a dynamic covalent cross-linked structure, 3 parts by weight of the bio-based hyperbranched polysiloxane obtained in step (I), 12 parts by weight of alumina nanoparticles with an average particle size of 80 nm, and 10 parts by weight of chopped glass fibers were added. The above materials were added to a twin-screw extruder and dynamically vulcanized melt-blended at 280°C and 200 rpm for 6 min. The resulting composite material was granulated and then injection molded at 240°C and 30 MPa for 45 s, followed by cooling for 2 min, with a total molding cycle of 4 min, to obtain the wear-resistant thermoplastic elastomer of Example 1.

[0031] Example 2 This embodiment provides a wear-resistant thermoplastic elastomer. This wear-resistant thermoplastic elastomer uses thermoplastic polyester elastomer as the base resin, employs a high content of bio-based hyperbranched polysiloxane and a high content of nano-ceramic particles to construct a wear-resistant interface layer, and incorporates a dynamic covalent network to improve structural stability and self-healing ability under frictional thermal conditions.

[0032] (I) Preparation of bio-based hyperbranched polysiloxanes Weigh out 50 parts glucose, 5 parts methyltriethoxysilane, 0.5 parts phosphoric acid, 5 parts epoxy acrylate and 10 parts DMSO by weight.

[0033] First, glucose and methyltriethoxysilane were mixed evenly and added to DMSO. The mixture was stirred at 100 rpm for 1 hour at 200°C. Then, phosphoric acid was added, and polycondensation was continued at 150°C for 6 hours. After the reaction was completed, epoxy acrylate was added for end modification. The system was then cooled to 20°C, the solvent was removed, and the mixture was dried at 80°C for 4 hours to obtain bio-based hyperbranched polysiloxane.

[0034] (II) Preparation of thermoplastic elastomer matrix with dynamic covalent crosslinking structure In this embodiment, the thermoplastic elastomer matrix accounts for 68.5% of the total mass of the final hyperbranched polysiloxane-modified wear-resistant thermoplastic elastomer, the bio-based hyperbranched polysiloxane accounts for 25% of the mass of the thermoplastic elastomer matrix, the nano-ceramic particles account for 20% of the mass of the thermoplastic elastomer matrix, and the chopped glass fibers account for 1% of the mass of the thermoplastic elastomer matrix. The microfiber structure formed after melt processing has an aspect ratio of 100:1 and a microfiber diameter of 6 μm.

[0035] Based on 100 parts by weight of thermoplastic polyester elastomer base resin, 1 part by weight of furan-terminated poly(adipate-butanediol) polyester diol is added as component A, 10 parts by weight of tetra-armed polyethylene glycol-maleimide is added as component B, 0.1 parts by weight of benzene-1,4-diboronic acid is added as component C, 10 parts by weight of polyisoprene-hydroxy polymer is added as component D, and 2 parts by weight of titanium trichloride is added as component E.

[0036] First, the thermoplastic polyester elastomer base resin, component A, and component D were mixed at 150°C and 50 rpm for 24 min. Then, under a nitrogen atmosphere, the temperature was raised to 120°C and pre-reacted at 300 rpm. Next, components B and C were added, and the reaction was carried out at 200°C for 1 h. Then, component E was added, and the reaction was catalytically carried out at 150°C for 4 h. After cooling to room temperature, a thermoplastic polyester elastomer matrix with a dynamically covalently crosslinked structure was obtained.

[0037] (III) Preparation of wear-resistant thermoplastic elastomers Based on 100 parts by mass of the above-mentioned thermoplastic elastomer matrix with a dynamic covalent cross-linked structure, 25 parts by mass of the bio-based hyperbranched polysiloxane obtained in step (I), 20 parts by mass of silicon nitride nanoparticles with an average particle size of 50 nm, and 1 part by mass of chopped glass fiber were added. The above materials were dynamically vulcanized and melt-blended at 150°C and 1000 rpm for 2 min. Then, they were injection molded at 180°C and 80 MPa for 15 s, cooled for 6 min, and the total molding cycle was 8 min, to obtain the wear-resistant thermoplastic elastomer of Example 2.

[0038] Example 3 This embodiment provides a wear-resistant thermoplastic elastomer. The wear-resistant thermoplastic elastomer uses a blend of thermoplastic polyurethane and thermoplastic polyamide elastomers as the base resin. While maintaining a dynamic covalent cross-linked structure, it employs a moderate content of hyperbranched polysiloxane and glass fiber, as well as a low content of nano-ceramic particles, to achieve a balance between wear resistance, resilience, and processing fluidity.

[0039] (I) Preparation of bio-based hyperbranched polysiloxanes Weigh out 28 parts of sorbitol, 30 parts of triethoxysilane acrylate, 2.5 parts of boron trifluoride, 3 parts of epichlorohydrin, and 100 parts of THF by weight.

[0040] First, sorbitol and triethoxysilane acrylate were mixed evenly and then added to THF. The mixture was stirred at 160°C and 500 rpm for 2.5 h. Then, boron trifluoride was added, and polycondensation was carried out at 200°C for 4.5 h. Epichlorohydrin was then added for end-functionalization modification. The reaction solution was cooled to 25°C, the solvent was removed, and the solution was dried at 70°C for 8 h to obtain bio-based hyperbranched polysiloxane.

[0041] (II) Preparation of thermoplastic elastomer matrix with dynamic covalent crosslinking structure In this embodiment, the thermoplastic elastomer matrix accounts for 83.33% of the total mass of the final hyperbranched polysiloxane-modified wear-resistant thermoplastic elastomer, the bio-based hyperbranched polysiloxane accounts for 12% of the mass of the thermoplastic elastomer matrix, the nano-ceramic particles account for 2% of the mass of the thermoplastic elastomer matrix, and the chopped glass fibers account for 6% of the mass of the thermoplastic elastomer matrix. The microfiber structure formed after melt processing has an aspect ratio of 72:1 and a microfiber diameter of 9 μm.

[0042] Based on 100 parts by weight of a blend base resin composed of thermoplastic polyurethane and thermoplastic polyamide elastomer in a mass ratio of 70:30, the following components are added: 8 parts by weight of furan-terminated polycarbonate diol as component A, 0.5 parts by weight of bismaleimide polyethylene glycol as component B, 8 parts by weight of 1,4-phenylenediborate bisnepentyl glycol ester as component C, 0.5 parts by weight of polyisoprene difunctional hydroxyl polymer as component D, and 0.01 parts by weight of ferric chloride as component E.

[0043] First, the base resin, component A, and component D were mixed at 180°C and 120 rpm for 30 min. Then, under a nitrogen atmosphere, the temperature was raised to 150°C and pre-reacted at 50 rpm. Next, components B and C were added, and the reaction was carried out at 175°C for 4 h. Then, component E was added, and the reaction was catalytically carried out at 200°C for 2.5 h. After cooling to room temperature, an elastomer matrix with a dynamically covalently cross-linked structure was obtained.

[0044] (III) Preparation of wear-resistant thermoplastic elastomers Based on 100 parts by mass of the above-mentioned thermoplastic elastomer matrix with a dynamic covalent cross-linked structure, 12 parts by mass of the bio-based hyperbranched polysiloxane obtained in step (I), 2 parts by mass of zirconium oxide nanoparticles with an average particle size of 100 nm, and 6 parts by mass of chopped glass fibers were added. The above raw materials were dynamically vulcanized and melt-blended at 220°C and 650 rpm for a residence time of 10 min. After blending, the mixture was injection molded at 210°C and 55 MPa for 60 s, cooled for 4 min, and the total molding cycle was 3 min, to obtain the wear-resistant thermoplastic elastomer of Example 3.

[0045] Comparative Example 1 The difference between this comparative example and Example 3 is that bio-based hyperbranched polysiloxane and its corresponding raw materials and preparation methods are not used. Instead, petroleum-based neutral polysiloxane is used as the siloxane modification component. The remaining components and process conditions are the same as in Example 3.

[0046] Specifically, based on 100 parts by weight of the dynamically covalently crosslinked matrix described in Example 3, 12 parts by weight of hydroxyl-terminated polydimethylsiloxane, 2 parts by weight of zirconium oxide nanoparticles with an average particle size of 100 nm, and 6 parts by weight of chopped glass fibers were added. The mixture was melt-blended at 220°C and 650 rpm for 10 min, then injection molded at 210°C and 55 MPa for 60 s, cooled for 4 min, with a total molding cycle of 3 min, to obtain the hyperbranched polysiloxane-modified wear-resistant thermoplastic elastomer prepared in Comparative Example 1. The polysiloxane used in this example has a linear structure.

[0047] Comparative Example 2 This comparative example uses only conventional thermoplastic elastomer resins to prepare the final material, without introducing dynamic covalent cross-linking structures, or adding hyperbranched polysiloxanes, nano-ceramic particles, or chopped glass fibers.

[0048] Specifically, 100 parts by weight of thermoplastic polyurethane was selected as the sole resin component. After being melt-plasticized at 200°C and 400 rpm for 5 minutes, it was injection molded at 210°C and 50 MPa for 30 seconds, and then cooled for 4 minutes to obtain the hyperbranched polysiloxane-modified wear-resistant thermoplastic elastomer prepared in Comparative Example 2. This comparative example used a basic thermoplastic elastomer material that had not undergone dynamic crosslinking modification or wear-resistant reinforcement modification.

[0049] Comparative Example 3 Compared to Example 3, this comparative example still employs the dynamic covalent modification approach, but only retains the preparation of the reversible Diels-Alder crosslinking structure, removing the borate ester dynamic crosslinking structure. That is, when preparing the dynamic crosslinked matrix, components A, B, and E are retained, while components C and D are not added. The remaining wear-resistant modifying components and molding process remain consistent with Example 3.

[0050] Specifically, based on 100 parts by mass of a blend base resin consisting of thermoplastic polyurethane and thermoplastic polyamide elastomer in a mass ratio of 70:30, 8 parts by mass of furan-terminated polycarbonate diol were added as a dynamic crosslinking precursor, 0.5 parts by mass of bismaleimide polyethylene glycol were added as a dienophilic crosslinking agent, and 0.01 parts by mass of ferric chloride were added as a catalyst. After mixing at 120 rpm for 30 min at 180 °C, pre-reacting at 150 °C, reacting at 175 °C for 4 h, catalyzing at 200 °C for 2.5 h, and cooling, a thermoplastic elastomer matrix containing only a single reversible Diels-Alder crosslinking structure was obtained.

[0051] Subsequently, based on 100 parts by mass of the matrix, 12 parts by mass of bio-based hyperbranched polysiloxane, 2 parts by mass of zirconium oxide nanoparticles with an average particle size of 100 nm, and 6 parts by mass of chopped glass fiber were added. The mixture was melt-blended at 220°C and 650 rpm for 10 min, and then injection-molded at 210°C and 55 MPa for 60 s, cooled for 4 min, with a total molding cycle of 3 min, to obtain the hyperbranched polysiloxane-modified wear-resistant thermoplastic elastomer prepared in Comparative Example 3.

[0052] To observe the microfiber structure, nanoparticle dispersion, and matrix cross-sectional morphology formed by melt shearing of chopped glass fibers in the wear-resistant thermoplastic elastomers obtained in Examples 1 to 3 and Comparative Examples 1 to 3, cross-sectional micromorphology tests were performed on each sample. Scanning electron microscopy was used for observation. Specifically, strips measuring 10mm × 5mm × 3mm were cut from the injection-molded elastomer samples prepared in Examples 1 to 3 and Comparative Examples 1 to 3, along the middle of the product. To preserve the true internal dispersion structure of the material as much as possible, a liquid nitrogen cryogenic fracture method was preferred for preparing the cross-section. That is, the cut sample was first placed in liquid nitrogen and frozen for 5 to 10 minutes, then a rapid external force was applied to cause it to fracture along the thickness direction, obtaining a relatively smooth, fresh cross-section. After fixing the obtained cross-section sample on the sample stage, gold sputtering was performed under vacuum conditions. The gold sputtering time was controlled to be 40 to 90 seconds to improve the surface conductivity of the sample and reduce the charging effect during observation. The cross-sections were then observed using a scanning electron microscope (SEM) of Hitachi SU 8010. The SEM was used at accelerating voltages of 3kV–10kV and magnifications of 1000x–10000x. The distribution of microfiber diameter and aspect ratio was statistically analyzed using image measurement software. This method allows for a relatively clear comparison of the degree of microfiber formation, interfacial bonding, uniformity of nanoceramic particle dispersion, and cross-sectional density in Examples 1–3 and Comparative Examples 1–3. This provides microscopic evidence for analyzing the influence of different formulations and network structures on the wear resistance and mechanical properties of the materials.

[0053] Figure 1 Microscopic morphology diagrams of Examples 1-3 are shown. Figure 2 Microscopic morphology diagrams of comparative examples 1-3 are shown. (From...) Figures 1-2As shown, in the cross-section of the sample from Example 1, the microfiber structure formed by the melt shearing of chopped glass fibers is quite obvious. The microfibers are relatively uniformly distributed in the matrix, locally interwoven, and tightly bonded to the surrounding matrix, indicating that the reinforcing phase in this example can be effectively dispersed and embedded inside the thermoplastic elastomer matrix. In the cross-section of the sample from Example 2, the microfiber structure is more slender, with more prominent orientation characteristics. The surrounding granular phase is finely dispersed, and the overall cross-section is relatively dense, indicating that under the combined action of a high content of hyperbranched polysiloxane and nano-ceramic particles, the internal reinforcing structure and interface distribution of the material are relatively stable. In the cross-section of the sample from Example 3, the microfiber structure is relatively evenly distributed, with the microfiber length and diameter at a moderate level. The matrix continuity is good, and no obvious large-scale agglomeration of the granular phase is observed, indicating that this example achieves a good balance between reinforcing phase dispersion, matrix toughness, and overall structural uniformity.

[0054] Although fibrous structures were still visible in the cross-section of Comparative Example 1, their uniformity of distribution and interfacial bonding were lower than those of Examples 1 to 3. Some areas showed discontinuous interfacial transitions, indicating that the compatibility and anchoring effect between the reinforcing phase and the matrix was weakened after using linear polysiloxane. The cross-section of Comparative Example 2 was predominantly matrix phase, with no obvious microfiber reinforcement structure. Locally, a relatively uniform continuous phase morphology was observed, indicating that without the introduction of relevant wear-resistant modifying components and dynamic network structures, the material lacked effective micro-reinforcing units. A certain number of fibrous structures were visible in the cross-section of Comparative Example 3, but its overall distribution, interfacial continuity, and cross-sectional density were still lower than those of Examples 1 to 3. This suggests that while retaining only the reversible Diels-Alder cross-linked structure in the preparation of the thermoplastic elastomer matrix could maintain the reinforcing structure to some extent, the overall microstructure stability remained limited.

[0055] Therefore, compared with Comparative Example 1, Examples 1 to 3, by using bio-based hyperbranched polysiloxanes instead of linear polysiloxanes, exhibit more uniform dispersion of the siloxane phase in the thermoplastic elastomer matrix. This facilitates the formation of a stable interface layer between the siloxane phase and the nano-ceramic particles and glass fibers, thus promoting the construction of a continuous wear-resistant protective layer during friction and improving the surface integrity of the material after repeated wear. Compared with Comparative Example 2, Examples 1 to 3 not only introduce wear-resistant modified components composed of hyperbranched polysiloxanes, nano-ceramic particles, and glass fibers, but also establish a reversible dynamic covalent network within the matrix. This enables the material to possess a certain network reconstruction capability under frictional heat, resulting in significant advantages in wear resistance, fatigue wear resistance, and long-term service stability. Compared with Comparative Example 3, the dual dynamic covalent crosslinking structures constructed in Examples 1 to 3 have both reversible Diels-Alder bonds and reversible borate ester bonds, resulting in a richer network response mode. They can provide more sufficient stress dissipation and structural recovery under different temperature and stress conditions. Therefore, their overall performance is superior to that of wear-resistant thermoplastic elastomers prepared from thermoplastic elastomer matrices containing only reversible Diels-Alder crosslinking structures.

[0056] The samples in Examples 1 to 3 and Comparative Examples 1 to 3 in Table 1 were all taken from injection-molded sheets or standard test pieces prepared under the same process conditions. Before testing, each group of samples was placed in an environment with a temperature of 23°C and a relative humidity of 50% for no less than 24 hours, and then cut according to the requirements of each test item. For tensile strength and elongation at break tests, dumbbell-shaped samples were preferably cut from the injection-molded sheet along the melt flow direction; for abrasion and coefficient of friction tests, samples with smooth surfaces and no obvious bubbles or defects were preferably cut from the same batch of molded sheets to reduce the influence of processing direction and surface defects on the test results.

[0057] The abrasion test was conducted according to GB / T 9867-2008 "Determination of Abrasion Resistance of Vulcanized Rubber or Thermoplastic Rubber - Rotary Roller Abrasion Tester Method". A DIN-type rotary roller abrasion tester was used. During the test, the samples were prepared to meet the standard requirements, and a rotary roller abrasion test was performed under specified load and abrasion stroke conditions. After the test, the abrasion amount was calculated based on the volume loss, and the unit can be expressed as mm. 3 .

[0058] The coefficient of friction was tested according to GB / T 3960-2016 "Test Method for Sliding Friction and Wear of Plastics". When sampling, samples with flat surfaces and no obvious defects can be cut from the middle of the injection molded sheets obtained in Examples 1 to 3 and Comparative Examples 1 to 3. During the test, the sampling direction, size and surface condition of each group of samples should be kept consistent to reduce the influence of processing direction and surface roughness on the coefficient of friction results.

[0059] The tensile strength and elongation at break are tested according to GB / T 1040.2-2006, "Determination of Tensile Properties of Plastics - Part 2: Test Conditions for Molded and Extruded Plastics". Injection-molded dumbbell-shaped specimens can be used. Before testing, the specimens should be conditioned according to GB / T 2918-2018, "Standard Environment for Conditioning and Testing of Plastic Specimens", to ensure data comparability between different samples. Both GB / T 1040.2-2006 and GB / T 2918-2018 are currently applicable or valid general standards for plastic testing. During testing, the specimen is clamped between tensile fixtures and stretched under standard conditions. The maximum tensile stress before fracture is recorded as the tensile strength, and the elongation at fracture is recorded as the elongation at break.

[0060] The self-healing rate was tested by first preparing standard specimens for each group of samples according to the tensile test specimen dimensions. The specimens were then cut at the center of the gauge length to 50% of their thickness. The cuts were then joined together, and the specimens were heat-treated at 80℃ for 2 hours, followed by placement at 23℃ for 12 hours. The tensile strength was then retested according to the tensile test conditions corresponding to GB / T 528-2009. The self-healing rate was calculated as the ratio of the repaired tensile strength to the original tensile strength multiplied by 100%. The test results are shown in Table 1. Table 1 As shown in Table 1, Examples 1 to 3 exhibit significantly lower wear and friction coefficients than Comparative Examples 1 to 3. This indicates that the synergistic construction of bio-based hyperbranched polysiloxane, nano-ceramic particles, chopped glass fibers, and a dynamically covalently cross-linked matrix in this application can effectively improve the surface stability and wear resistance of the material during friction. Specifically, Example 2 shows a wear of 52 mm. 3 The friction coefficient was 0.24, the best among all groups, which is related to its high content of hyperbranched polysiloxane and nano-ceramic particles. The former is conducive to the formation of a more stable low-shear surface layer at the friction interface, while the latter improves the surface layer's resistance to cutting and plastic deformation. Therefore, this embodiment performs better in reducing wear and frictional resistance. In contrast, Comparative Example 2 did not introduce wear-resistant modifying components or construct a dynamic reversible network, and its wear reached 126 mm. 3 The coefficient of friction reaches 0.46, indicating that it is difficult to maintain a stable structure under continuous friction by relying solely on conventional thermoplastic elastomer matrices.

[0061] From a mechanical property perspective, the tensile strength and elongation at break of Examples 1 to 3 were generally superior to those of the comparative example. Example 1 achieved a tensile strength of 34.8 MPa, the highest among all groups, indicating that the higher content of chopped glass fibers, after melt processing to form a microfiber-reinforced structure, could more effectively withstand external forces and inhibit crack propagation. Example 3 achieved an elongation at break of 560%, the highest among all groups, indicating a better balance between reinforcement and flexibility. These results demonstrate that this application does not simply rely on rigid fillers to improve wear resistance, but rather establishes a relatively coordinated structural relationship between the reinforcing phase, flexible matrix, and dynamic reversible network, enabling the material to maintain good deformability while improving strength. Although Comparative Example 1 retained nano-ceramic particles and glass fibers, the use of linear polysiloxane instead of bio-based hyperbranched polysiloxane reduced interfacial anchoring and network penetration, resulting in a tensile strength of only 28.4 MPa and an elongation at break of 455%, both lower than Example 3. Although Comparative Example 3 retained the wear-resistant modified components, the thermoplastic elastomer matrix prepared therein only had a reversible Diels-Alder crosslinking structure. Its tensile strength and elongation at break were 26.9 MPa and 472%, respectively, which were still lower than those of Examples 1 to 3. This indicates that the dual dynamic covalent crosslinking structure has a positive effect on maintaining the structural integrity of the material during the stress process.

[0062] Examples 1 to 3 achieved self-healing rates of 86%, 82%, and 89%, respectively, significantly higher than Comparative Example 1 (71%), Comparative Example 3 (63%), and Comparative Example 2 (18%). This indicates that under frictional heat or external thermal stimulation, the dynamic covalent bonds within the material can undergo reversible dissociation and recombination, thereby achieving rebinding and performance recovery of the damaged area. Example 3, in particular, exhibited the highest self-healing rate, indicating a good match between its dynamic network configuration and the external wear-resistant modification components, maintaining wear resistance while also endowing the material with high damage repair capabilities. Comparative Example 2, lacking a dynamic covalent crosslinking structure, had a self-healing rate of only 18%, essentially lacking effective repair capabilities. Although Comparative Example 3 retained some dynamic crosslinking capabilities, the simplified network type resulted in limited structural recovery after repair, leading to a self-healing rate of only 63%, still significantly lower than Examples 1 to 3.

[0063] The above results demonstrate that the wear-resistant thermoplastic elastomer provided in this application does not rely on a single filler or a single crosslinking method to achieve performance improvement. Instead, it achieves this through interfacial regulation via bio-based hyperbranched polysiloxanes, enhanced wear resistance via nano-ceramic particles, microfiber reinforcement via chopped glass fibers, and reversible reconfiguration capabilities via a dynamically covalently crosslinked matrix. This results in a good overall balance between wear resistance, frictional stability, mechanical strength, ductility, and self-healing ability. Example 1 emphasizes strength and reinforcement, Example 2 emphasizes friction reduction and wear resistance, and Example 3 demonstrates a more balanced overall performance, indicating that the technical solution of this application has good controllability and stable performance improvement effects.

[0064] The accompanying drawings of the embodiments disclosed in this invention only involve the technical features involved in the embodiments disclosed in this invention. Other technical features or means can be referred to in the general design. In the absence of conflict, the same embodiment and different embodiments of this invention can be combined with each other. The above description is only a preferred embodiment of this invention and is not intended to limit this invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of this invention should be included within the protection scope of this invention.

Claims

1. A hyperbranched polysiloxane-modified wear-resistant thermoplastic elastomer, characterized in that, The thermoplastic elastomer is composed of a wear-resistant composite material, which includes: The thermoplastic elastomer matrix accounts for 68.5% to 83.33% of the total mass of the composite material. A wear-resistant modifying component dispersed in the thermoplastic elastomer matrix, the wear-resistant modifying component comprising: Hyperbranched polysiloxanes, with a mass of 3% to 25% of the thermoplastic elastomer matrix; Nano-ceramic particles with a particle size of 50–100 nm, whose mass is 2%–20% of the thermoplastic elastomer matrix; and Short-cut glass fibers, with a mass of 1% to 10% of the thermoplastic elastomer matrix; The hyperbranched polysiloxane forms a semi-interpenetrating polymer network with the thermoplastic elastomer matrix, and the chopped glass fibers form microfiber structures in situ during the melt processing and are dispersed in the matrix; the aspect ratio of the microfiber structure is (50:1) to (100:1), the diameter distribution range of the microfibers is 6μm to 13μm, and the microfibers are distributed in a three-dimensional network in the matrix.

2. The wear-resistant thermoplastic elastomer according to claim 1, characterized in that, The thermoplastic elastomer matrix is ​​at least one of thermoplastic polyurethane, thermoplastic polyester elastomer, thermoplastic polyamide elastomer, or styrene-based thermoplastic elastomer; the hyperbranched polysiloxane is a bio-based hyperbranched polysiloxane, which contains reactive functional groups at its ends, wherein the reactive functional groups are selected from hydroxyl, amino, or epoxy groups, and the bio-based carbon content is not less than 25% (i.e., the carbon content in the bio-based polyol is not less than 25%). The raw materials for preparing the bio-based hyperbranched polysiloxane include, by weight: 10-50 parts by weight of bio-based polyol, wherein the bio-based polyol is selected from one or more of glycerol, glucose, plant-derived polyols, citric acid, lactic acid or their derivatives; 5-30 parts by weight of silane coupling agent, wherein the silane coupling agent is selected from one or more of methyltriethoxysilane, aminotriethoxysilane, vinyltrichlorosilane or triethoxysilane acrylate; 0.5 to 5 parts by weight of acid catalyst, wherein the acid catalyst includes, but is not limited to, sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, phosphoric acid or boron trifluoride; 1 to 5 parts by weight of a reactive functional group modifier, wherein the reactive functional group modifier includes, but is not limited to, isocyanate compounds, epoxy compounds, carboxylic acid compounds or aldehyde compounds; The organic solvent is 10 to 100 parts by weight, wherein the organic solvent is an ether organic solvent, chloroform or anhydrous ethanol, and the ether organic solvent includes, but is not limited to, tetrahydrofuran or dimethyl thionamide.

3. The wear-resistant thermoplastic elastomer according to claim 2, characterized in that, The preparation method of the bio-based hyperbranched polysiloxane includes the following steps: A1: Mix the bio-based polyol and the silane coupling agent in the specified weight parts evenly to obtain a reaction mixture; A2: Add the reaction mixture obtained in step A1 to the organic solvent in the specified weight, heat to 120-200°C, and stir continuously at 100-500 rpm for 1-4 hours; A3: Add the acid catalyst in the specified weight amount to the reaction intermediate obtained in step A2, and continue heating to 150-200°C to allow the reaction to undergo polycondensation and form hyperbranched polysiloxane. The reaction time is 3-6 hours. A4: After the reaction in step A3 is completed, the reactive functional group modifier in the specified weight parts is added to the reaction product of step A3 to terminate the reaction and end-functionalize the hyperbranched polysiloxane. A5: After the reaction is complete, the system is cooled to 20-30℃, and then excess organic solvent is slowly removed to obtain a bio-based hyperbranched polysiloxane preproduct. The preproduct is then dried at 60-80℃ for 4-12 hours to obtain the bio-based hyperbranched polysiloxane.

4. The wear-resistant thermoplastic elastomer according to claim 1, characterized in that, The isocyanate compound is one or more of methyl isocyanate and toluene-2,4-diisocyanate, and is used to react with amino groups; The epoxy compound is one or more of epoxy acrylate and epichlorohydrin, and is used to react with hydroxyl groups; The carboxylic acid compound is one or more of benzoic acid and adipic acid, and is used to react with amino groups; The aldehyde compound is one or more of formaldehyde and pentenal, and is used to react with amino and hydroxyl groups.

5. The wear-resistant thermoplastic elastomer according to claim 1, characterized in that, The nano-ceramic particles are one or more of silicon nitride nanoparticles, aluminum nitride nanoparticles, alumina, silicon carbide nanoparticles, or zirconium oxide nanoparticles.

6. The wear-resistant thermoplastic elastomer according to claim 1, characterized in that, The thermoplastic elastomer matrix is ​​a thermoplastic elastomer matrix with a dynamically covalently cross-linked structure, which is formed by preparing the following raw material components: The difunctionalized copolymer component A containing a reversible Diels-Alder structure is used in an amount of 1% to 15% by weight of the thermoplastic elastomer matrix. The difunctionalized copolymer component A is a polyether polyol with furan end groups or a polyether polyol or polyester polyol with furan end groups. The amount of dienophilic crosslinking agent component B, by weight, is 0.5% to 10% of the mass of the thermoplastic elastomer matrix; the dienophilic crosslinking agent component B is a maleimide difunctionalized small molecule or a polymer containing dimaleimide groups; The diboronic acid crosslinking agent component C, by weight, is used in an amount of 0.1% to 8% of the mass of the thermoplastic elastomer matrix, wherein the diboronic acid crosslinking agent component C is phenyl 1,4-diboronic acid or its ester derivative. The hydroxyl functional modification component D, by weight, is used in an amount of 0.5% to 10% of the mass of the thermoplastic elastomer matrix, wherein the hydroxyl functional modification component D is a modified isoprene in which 1,2-diol or 1,3-diol segments can be introduced. Catalyst component E, by weight, is used in an amount of 0.01% to 2% of the mass of the thermoplastic elastomer matrix, and catalyst component E is a Lewis acid catalyst; The amount of the thermoplastic elastomer matrix is ​​as defined in claim 1.

7. The wear-resistant thermoplastic elastomer according to claim 6, characterized in that, The method for preparing the thermoplastic elastomer matrix with the dynamically covalently crosslinked structure includes: 1) Mix the corresponding mass of thermoplastic elastomer matrix with the corresponding mass of the difunctional copolymer component A and the corresponding mass of the hydroxyl functional modified component D in a mixer at a temperature of 80-180°C and a speed of 50-200 rpm for 10-30 minutes to achieve uniform mixing. 2) Heat the mixture to 120–180°C under a nitrogen atmosphere and stir at 50–300 rpm to allow the matrix and component D to pre-react; 3) Add the appropriate mass of the dienophilic crosslinking agent component B and the appropriate mass of the diboronic acid crosslinking agent component C to the mixture obtained in step 2), and react at 140-200°C for 1-6 hours to form a dynamic covalent crosslinking network with reversible Diels-Alder reversible crosslinking points and borate ester reversible crosslinking points; 4) Add the appropriate mass of the catalyst component E to the mixture obtained in step 3), and carry out the catalytic crosslinking reaction at 150~200℃ for 1~4 hours; 5) Finally, the product obtained in step 4) is cooled to room temperature to obtain a thermoplastic elastomer matrix with a dynamic covalent crosslinking structure, wherein the dynamic covalent crosslinking structure can be thermally reversed and recombined.

8. The wear-resistant thermoplastic elastomer according to claim 6, characterized in that, The thermoplastic elastomer matrix is ​​at least one of thermoplastic polyurethane, thermoplastic polyester elastomer, thermoplastic polyamide elastomer, or styrene-based thermoplastic elastomer; The difunctionalized copolymer component A is furan-terminated polytetrahydrofuran diol, furan-terminated polypropylene glycol diol, furan-terminated polycaprolactone diol, furan-terminated polycarbonate diol, and furan-terminated poly(adipate-butanediol) polyester diol. The dienophilic crosslinking agent component B is 1,4-bis(maleimide)butane or 1,6-bismaleimidehexane. 、 One or more of bismaleimide polyethylene glycol, four-armed polyethylene glycol-maleimide, or eight-armed polyethylene glycol-maleimide; The binary boric acid crosslinking agent component C is one or more of phenyl-1,4-diboronic acid, phenyl-1,4-diboronic acid methyliminodiacetic acid ester, 1,4-phenyldiboronic acid bis(neopentyl glycol) ester or phenyl-1,4-diboronic acid methyliminodiacetic acid ester. The hydroxyl functional modification component D is one or more of hydroxyl-terminated polyisoprene diol, polyisoprene-based hydroxyl polymer, or polyisoprene difunctional hydroxyl polymer. The catalyst component E is one or more of aluminum trifluoride, zinc chloride, boron chloride, ferric chloride, boron trifluoride, titanium trichloride, or phosphorus pentachloride.

9. A method for preparing a hyperbranched polysiloxane-modified wear-resistant thermoplastic elastomer as described in any one of claims 1-8, characterized in that, Includes the following steps: S1: Using bio-based polyols as the core molecule, terminally functionalized hyperbranched polysiloxanes are synthesized through stepwise polycondensation reactions. S2: The thermoplastic elastomer matrix of a corresponding mass fraction, the chopped glass fiber of a corresponding mass fraction, the hyperbranched polysiloxane prepared in step S1 of a corresponding mass fraction, and the nano-ceramic particles with a particle size of 50-100 nm of a corresponding mass fraction are dynamically vulcanized and melt-blended in an extruder. The temperature of the dynamic vulcanization and melt blending is 150℃-280℃, the screw speed is 200rpm-1000rpm, and the residence time is 2min-10min, so that the nano-ceramic particles and chopped glass fiber are uniformly dispersed in the thermoplastic elastomer matrix, and at the same time, a wear-resistant thermoplastic elastomer composite material is formed. S3: The wear-resistant thermoplastic elastomer composite material obtained in step S2 is molded into the wear-resistant thermoplastic elastomer.

10. The preparation method according to claim 9, characterized in that, The compression molding step includes: injecting the wear-resistant thermoplastic elastomer composite material obtained in step S2 into the mold within 15 seconds to 60 seconds at an injection pressure of 180℃~240℃ and 30MPa~80MPa, and cooling for 2min~6min after injection to complete the compression molding; the compression molding cycle from injection to cooling is 3min~8min.

Images